Process of making alkylaromatics using EMM-12

ABSTRACT

This disclosure relates to a process for manufacturing a mono-alkylaromatic compound, said process comprising contacting a feedstock comprising an alkylatable aromatic compound and an alkylating agent under alkylation reaction conditions with a catalyst comprising EMM-12, wherein said EMM-12 is a molecular sieve having, in its as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks having a d-spacing maximum in the range of 14.17 to 12.57 Angstroms, a d-spacing maximum in the range of 12.1 to 12.56 Angstroms, and non-discrete scattering between about 8.85 to 11.05 Angstroms or exhibit a valley in between the peaks having a d-spacing maximum in the range of 10.14 to 12.0 Angstroms and a d-spacing maximum in the range from 8.66 to 10.13 Angstroms with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima in the range of 10.14 to 12.0 Angstroms and in the range from 8.66 to 10.13 Angstroms.

PRIORITY CLAIM

This application is a National Stage Application of InternationalApplication No. PCT/US2009/050727 filed Jul. 15, 2009, which claims thebenefit of U.S. Provisional Application Ser. No. 61/084,166 filed Jul.28, 2008, both of which are hereby incorporated by reference in theirentirety.

FIELD OF THE INVENTION

The present disclosure relates to a process for producing alkylaromaticcompounds, especially mono-alkylaromatic compounds, for exampleethylbenzene, cumene and sec-butylbenzene, using a molecular sievecomposition designated as EMM-12 which is an MCM-22 family materialhaving unique XRD features.

BACKGROUND OF THIS DISCLOSURE

Molecular sieve materials, both natural and synthetic, have beendemonstrated in the past to have catalytic properties for various typesof hydrocarbon conversion. Molecular sieves that find application incatalysis include any of the naturally occurring or syntheticcrystalline molecular sieves. Examples of these zeolites include largepore zeolites, intermediate pore size zeolites, and small pore zeolites.These zeolites and their isotypes are described in “Atlas of ZeoliteFramework Types”, eds. W. H. Meier, D. H. Olson and Ch. Baerlocher,Elsevier, Fifth Edition, 2001, which is hereby incorporated byreference. A large pore zeolite generally has a pore size of at leastabout 7 Å and includes LTL, VFI, MAZ, FAU, OFF, *BEA, and MOR frameworktype zeolites (IUPAC Commission of Zeolite Nomenclature). Examples oflarge pore zeolites include mazzite, offretite, zeolite L, VPI-5,zeolite Y, zeolite X, omega, and Beta. An intermediate pore size zeolitegenerally has a pore size from about 5 Å to less than about 7 Å andincludes, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW,and TON framework type zeolites (IUPAC Commission of ZeoliteNomenclature). Examples of intermediate pore size zeolites includeZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite 1, and silicalite 2. A smallpore size zeolite has a pore size from about 3 Å to less than about 5.0Å and includes, for example, CHA, ERI, KFI, LEV, SOD, and LTA frameworktype zeolites (IUPAC Commission of Zeolite Nomenclature). Examples ofsmall pore zeolites include ZK-4, ZSM-2, SAPO-34, SAPO-35, ZK-14,SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite, zeolite T,gmelinite, ALPO-17, and clinoptilolite.

U.S. Pat. No. 4,439,409 refers to a crystalline molecular sievecomposition of matter named PSH-3 and its synthesis from a reactionmixture for hydrothermal reaction containing hexamethyleneimine, anorganic compound which acts as directing agent for synthesis of theMCM-56 (U.S. Pat. No. 5,362,697). Hexamethyleneimine is also taught foruse in synthesis of crystalline molecular sieves MCM-22 (U.S. Pat. No.4,954,325) and MCM-49 (U.S. Pat. No. 5,236,575). A molecular sievecomposition of matter referred to as zeolite SSZ-25 (U.S. Pat. No.4,826,667) is synthesized from a reaction mixture for hydrothermalreaction containing an adamantane quaternary ammonium ion. U.S. Pat. No.6,077,498 refers to a crystalline molecular sieve composition of matternamed ITQ-1 and its synthesis from a reaction mixture for hydrothermalreaction containing one or a plurality of organic additives.

U.S. patent application Ser. No. 11/823,129 discloses a molecular sievecomposition designated as EMM-10-P, having, in its as-synthesized form,an X-ray diffraction pattern including d-spacing maxima at 13.18±0.25and 12.33±0.23 Angstroms, wherein the peak intensity of the d-spacingmaximum at 13.18±0.25 Angstroms is at least as great as 90% of the peakintensity of the d-spacing maximum at 12.33±0.23 Angstroms. U.S. patentapplication Ser. No. 11/824,742 discloses a molecular sieve compositiondesignated as EMM-10, in its ammonium exchanged form or in its calcinedform, comprising unit cells with MWW topology, said crystallinemolecular sieve is characterized by diffraction streaking from the unitcell arrangement in the c direction. The crystalline molecular sieve isfurther characterized by the arced hk0 patterns of electron diffractionpattern. The crystalline molecular sieve is further characterized by thestreaks in the electron diffraction pattern along the c* direction. U.S.patent application Ser. No. 11/827,953 discloses a crystalline MCM-22family molecular sieve having, in its as-synthesized form, an X-raydiffraction pattern including a peak at d-spacing maximum of 12.33±0.23Angstroms, a distinguishable peak at a d-spacing maximum between 12.57to about 14.17 Angstroms and a non-discrete peak at a d-spacing maximumbetween 8.8 to 11 Angstroms, wherein the peak intensity of the d-spacingmaximum between 12.57 to about 14.17 Angstroms is less than 90% of thepeak intensity of the d-spacing maximum at 12.33±0.23 Angstroms.

The term “MCM-22 family material” (or “material of the MCM-22 family” or“molecular sieve of the MCM-22 family”), as used herein, includes:

-   (i) molecular sieves made from a common first degree crystalline    building block “unit cell having the MWW framework topology”. A unit    cell is a spatial arrangement of atoms which is tiled in    three-dimensional space to describe the crystal as described in the    “Atlas of Zeolite Framework Types”, Fifth edition, 2001, the entire    content of which is incorporated as reference;-   (ii) molecular sieves made from a common second degree building    block, a 2-dimensional tiling of such MWW framework type unit cells,    forming a “monolayer of one unit cell thickness”, preferably one    c-unit cell thickness;-   (iii) molecular sieves made from common second degree building    blocks, “layers of one or more than one unit cell thickness”,    wherein the layer of more than one unit cell thickness is made from    stacking, packing, or binding at least two monolayers of one unit    cell thick of unit cells having the MWW framework topology. The    stacking of such second degree building blocks can be in a regular    fashion, an irregular fashion, a random fashion, or any combination    thereof; or-   (iv) molecular sieves made by any regular or random 2-dimensional or    3-dimensional combination of unit cells having the MWW framework    topology.

The MCM-22 family materials are characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 3.57±0.07and 3.42±0.07 Angstroms (either calcined or as-synthesized). The MCM-22family materials may also be characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms (either calcined or as-synthesized).The X-ray diffraction data used to characterize the molecular sieve areobtained by standard techniques using the K-alpha doublet of copper asthe incident radiation and a diffractometer equipped with ascintillation counter and associated computer as the collection system.Materials belong to the MCM-22 family include MCM-22 (described in U.S.Pat. No. 4,954,325), PSH-3 (described in U.S. Pat. No. 4,439,409),SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described inEuropean Patent No. 0293032), ITQ-1 (described in U.S. Pat. No.6,077,498), ITQ-2 (described in International Patent Publication No.W097/17290), ITQ-30 (described in International Patent Publication No.WO2005118476), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49(described in U.S. Pat. No. 5,236,575), MCM-56 (described in U.S. Pat.No. 5,362,697), EMM-10-P (described in U.S. patent application Ser. No.11/823,129) and EMM-10 (described in U.S. patent application Ser. No.11/824,742). The entire contents of the patents are incorporated hereinby reference.

It is to be appreciated the MCM-22 family molecular sieves describedabove are distinguished from conventional large pore zeolite alkylationcatalysts, such as mordenite, in that the MCM-22 materials have 12-ringsurface pockets which do not communicate with the 10-ring internal poresystem of the molecular sieve.

The zeolitic materials designated by the IZA-SC as being of the MWWtopology are multi-layered materials which have two pore systems arisingfrom the presence of both 10 and 12 membered rings. The Atlas of ZeoliteFramework Types classes five differently named materials as having thissame topology: MCM-22, ERB-1, ITQ-1, PSH-3, and SSZ-25.

The MCM-22 family molecular sieves have been found to be useful in avariety of hydrocarbon conversion processes. Examples of MCM-22 familymolecular sieve are MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25, andERB-1. Such molecular sieves are useful for alkylation of aromaticcompounds. For example, U.S. Pat. No. 6,936,744 discloses a process forproducing a mono-alkylaromatic compound, particularly cumene, comprisingthe step of contacting a polyalkylated aromatic compound with analkylatable aromatic compound under at least partial liquid phaseconditions and in the presence of a transalkylation catalyst to producethe mono-alkylaromatic compound, wherein the transalkylation catalystcomprises a mixture of at least two different crystalline molecularsieves, wherein each of the molecular sieves is selected from zeolitebeta, zeolite Y, mordenite and a material having an X-ray diffractionpattern including d-spacing maxima at 12.4±0.25, 6.9±0.15, 3.57±0.07 and3.42±0.07 Angstroms.

A report by J. Ruan, P. Wu, B. Slater, L. Wu, J. Xiao, Y. Liu, M. He, O.Terasaki at the 15 IZA Conference in Beijing in 2007 disclosed ISE-MWWand ISE-FER materials, the former made from MCM-22-P material asstarting material. U.S. Patent Application Publication 2005/0158238 toTatsumi et al. disclosed MWW type zeolite substance. U.S. PatentApplication Publication 2004/0092757 to Oguchi et al. disclosedcrystalline MWW type titanosilicate catalyst. A report by W. Fan, P. Wu,S. Namba, and T. Tatsumi (J. Catalyst 243 (2006) 183-191) disclosed anew titanosilicate molecular sieve with the structure analogous toMWW-type lamellar precursor. J. Ruan, P. Wu B. Slater and O. Terasakidisclosed detailed structure of Ti-YNU-1 (Angew. Chem. Int. Ed., 2005,44, 6719) similar to ISE-MWW.

These closely related materials may further be distinguished bycomparing XRD diffraction patterns for d-spacing maxima corresponding to(002), (100), (101) and (102) reflections for both as-synthesized andcalcined materials. The d-spacing maximum corresponding to (002)reflection is typically in the range from 14.17 to 12.57 Angstroms(˜6.15-7.05 deg 2-θ Cu Kα radiation). The d-spacing maximumcorresponding to (100) reflection is typically in the range from 12.1 to12.56 Angstroms (˜7.3-7.05 deg 2-θ). The d-spacing maximum correspondingto (101) reflection is typically in the range from 10.14 to 12.0Angstroms (8.7-7.35 deg 2-θ). The d-spacing maximum corresponding to(102) reflection is typically in the range from 8.66 to 10.13 Angstroms(10.2-8.7 deg 2-θ). The following table (Table 1) summarizes thedifferences between MCM-22, MCM-49, EMM-10, MCM-56 and thetitanosilicate material reported by Tatsumi et al. based on theexistence and/or the feature of XRD diffraction pattern for d-spacingmaxima corresponding to (002), (100), (101) and (102) reflections forboth as-synthesized and calcined materials.

TABLE 1 As-synthesized Calcined XRD (002) (100) (101) (102) (002) (100)(101) (102) MCM-22 MCM-22-P MCM-22 Yes Yes Yes Yes No Yes Yes Yes Allfour peaks are resolved. A valley Peak corresponding to (002) is notexists between (101) and (102), wherein visible. All other three peaksare the measured intensity corrected for resolved. A valley existsbetween background at the lowest point being (101) and (102), whereinthe less than 50% of the point at the same measured intensity correctedfor XRD d-spacing on the line connecting background at the lowest pointbeing maxima for (101) and (102). less than 50% of the point at the sameXRD d-spacing on the line connecting maxima for (101) and (102). EMM-10EMM-10-P EMM-10 Yes Yes Non-discrete Yes Yes Non-discrete Both (002)peak and (100) peak are Peak corresponding to (002) is not resolved,wherein the peak intensity for visible. Peak corresponding to (100)(002) is at least as great as 90% of the is well resolved. peakintensity of the d-spacing And, maximum for (100). peaks correspondingto (101) and Further, (102) are non-discrete or exhibit a peakscorresponding to (101) and (102) valley but with measured intensity arenon-discrete or exhibit a valley but corrected for background at thewith measured intensity corrected for lowest point being not less than50% background at the lowest point being of the point at the same XRD d-not less than 50% of the point at the spacing on the line connectingsame XRD d-spacing on the line maxima for (101) and (102). connectingmaxima for (101) and (102). MCM-22 As-synthesized Calcined family YesYes Yes Yes No Yes Yes Yes material as Peaks corresponding to (002) and(100) Peak corresponding to (002) is not disclosed are well resolvedvisible. All other three peaks are in U.S. And, resolved. A valleyexists between patent peaks corresponding to (101) and (102) (101) and(102), wherein the application are non-discrete peaks at a d-spacingmeasured intensity corrected for No. maximum between 8.8 to 11background at the lowest point being 11/827,953 Angstroms, wherein thepeak intensity less than 50% of the point at the of the (002) is lessthan 90% of the peak same XRD d-spacing on the line intensity of the(100). connecting maxima for (101) and (102). MCM-49 MCM-49-P MCM-49 NoYes Yes Yes No Yes Yes Yes Peak corresponding to (002) is not Peakcorresponding to (002) is not visible or as a shoulder peak. Peakvisible or as a shoulder peak. Peak corresponding to (100) is wellresolved. corresponding to (100) is well And, resolved. peakscorresponding to (101) and (102) And, are resolved or exhibit a valleybut with peaks corresponding to (101) and measured intensity correctedfor (102) are resolved or exhibit a valley background at the lowestpoint being but with measured intensity corrected not greater than 50%of the point at the for background at the lowest point same XRDd-spacing on the line being not greater than 50% of the connectingmaxima for (101) and (102). point at the same XRD d-spacing on the lineconnecting maxima for (101) and (102). MCM-56 MCM-56-P MCM-56 No Yesnon-discrete No Yes non-discrete Peak corresponding to (002) is not Peakcorresponding to (002) is not visible. Peak corresponding to (100) isvisible. Peak corresponding to (100) well resolved. Peaks correspondingto is well resolved. Peaks corresponding (101) and (102) arenon-discrete to (101) and (102) are non-discrete or scattering. exhibita valley but with measured intensity corrected for background at thelowest point being not less than 50% of the point at the same XRDd-spacing on the line connecting maxima for (101) and (102). MWWPrecursor (US Patent Publication Calcined (US Patent Publicationmaterial 20050158238, FIG. 4) 20050158238 FIG. 2) Yes Yes Yes Yes No YesYes Yes All four peaks are resolved. A valley Only three peaks areresolved. A exists between (101) and (102), wherein valley existsbetween (101) and the measured intensity corrected for (102), whereinthe measured background at the lowest point being intensity correctedfor background at less than 50% of the point at the same the lowestpoint being less than 50% XRD d-spacing on the line connecting of thepoint at the same XRD d- maxima for (101) and (102). spacing on the lineconnecting maxima for (101) and (102). Ti-MCM-22 Precursor (J. Catal.,Table 1) Calcined (US20050158238 FIG. 1) Yes Yes Yes Yes Yes/No Yes YesYes All four peaks reported for Si/Ti = 106. All four peaks are resolvedfor Si/Ti higher than 70. Only three peaks for Si/Ti less than 70. Avalley exists between (101) and (102), wherein the measured intensitycorrected for background at the lowest point being less than 50% of thepoint at the same XRD d- spacing on the line connecting maxima for (101)and (102).

It is known that crystal morphology, size and aggregation/agglomeration,or new x-ray diffraction can affect catalyst behavior, especiallyregarding catalyst activity and stability.

The alkylaromatic compounds ethylbenzene and cumene, for example, arevaluable commodity chemicals which are used industrially for theproduction of styrene monomer and co-production of phenol and acetonerespectively. In fact, a common route for the production of phenolcomprises a process which involves alkylation of benzene with propyleneto produce cumene, followed by oxidation of the cumene to thecorresponding hydroperoxide, and then cleavage of the hydroperoxide toproduce equal molar amounts of phenol and acetone. Ethylbenzene may beproduced by a number of different chemical processes. One process whichhas achieved a significant degree of commercial success is the vaporphase alkylation of benzene with ethylene in the presence of a solid,acidic ZSM-5 zeolite catalyst. Examples of such ethylbenzene productionprocesses are described in U.S. Pat. Nos. 3,751,504 (Keown), 4,547,605(Kresge) and 4,016,218 (Haag).

Another process which has achieved significant commercial success is theliquid phase process for producing ethylbenzene from benzene andethylene since it operates at a lower temperature than the vapor phasecounterpart and hence tends to result in lower yields of by-products.For example, U.S. Pat. No. 4,891,458 (Innes) describes the liquid phasesynthesis of ethylbenzene with zeolite Beta, whereas U.S. Pat. No.5,334,795 (Chu) describes the use of MCM-22 in the liquid phasesynthesis of ethylbenzene.

Cumene has for many years been produced commercially by the liquid phasealkylation of benzene with propylene over a Friedel-Crafts catalyst,particularly solid phosphoric acid or aluminum chloride. More recently,however, zeolite-based catalyst systems have been found to be moreactive and selective for propylation of benzene to cumene. For example,U.S. Pat. No. 4,992,606 (Kushnerick) describes the use of MCM-22 in theliquid phase alkylation of benzene with propylene.

Existing alkylation processes for producing alkylaromatic compounds, forexample ethylbenzene and cumene, inherently produce polyalkylatedspecies as well as the desired monoalkyated product. It is thereforenormal to transalkylate the polyalkylated species with additionalaromatic feed, for example benzene, to produce additional monoalkylatedproduct, for example ethylbenzene or cumene, either by recycling thepolyalkylated species to the alkylation reactor or, more frequently, byfeeding the polyalkylated species to a separate transalkylation reactor.Examples of catalysts which have been used in the alkylation of aromaticspecies, such as alkylation of benzene with ethylene or propylene, andin the transalkylation of polyalkylated species, such aspolyethylbenzenes and polyisopropylbenzenes, are listed in U.S. Pat. No.5,557,024 (Cheng) and include MCM-49, MCM-22, PSH-3, SSZ-25, zeolite X,zeolite Y, zeolite Beta, acid dealuminized mordenite and TEA-mordenite.Transalkylation over a small crystal (<0.5 micron) form of TEA-mordeniteis also disclosed in U.S. Pat. No. 6,984,764 (Roth et al).

Where the alkylation step is performed in the liquid phase, it is alsodesirable to conduct the transalkylation step under liquid phaseconditions. However, by operating at relatively low temperatures, liquidphase processes impose increased requirements on the catalyst,particularly in the transalkylation step where the bulky polyalkylatedspecies must be converted to additional monoalkylated product withoutproducing unwanted by-products. This has proven to be a significantproblem in the case of cumene production where existing catalysts haveeither lacked the desired activity or have resulted in the production ofsignificant quantities of by-products such as ethylbenzene andn-propylbenzene.

There is, therefore, a need for a new process of producing alkylaromaticcompounds, especially mono-alkylaromatic compounds, with crystallinemolecular sieve.

SUMMARY OF THIS DISCLOSURE

In some embodiments, this disclosure relates to an alkylation process ofproducing mono-alkylaromatic compounds using a catalyst comprisingEMM-12 molecular sieve, wherein the EMM-12 molecular sieve has, in itsas-synthesized form and in calcined form, an X-ray diffraction patternincluding peaks having a d-spacing maximum in the range of 14.17 to12.57 Angstroms (˜6.15-7.05 deg 2-θ Cu Kα), a d-spacing maximum in therange of 12.1 to 12.56 Angstroms (˜7.3-7.05 deg 2-θ Cu Kα), andnon-discrete scattering between about 8.66 to 12.0 Angstroms or exhibita valley in between the peaks having a d-spacing maximum in the range of10.14 to 12.0 Angstroms (8.7-7.35 deg 2-θ Cu Kα) and a d-spacing maximumin the range from 8.66 to 10.13 Angstroms (10.2-8.7 deg 2-θ) but withmeasured intensity corrected for background at the lowest point beingnot less than 50% of the point at the same XRD d-spacing on the lineconnecting maxima in the range of 10.14 to 12.0 Angstroms (8.7-7.35 deg2-θ Cu Kα) and in the range from 8.66 to 10.13 Angstroms (10.2-8.7 deg2-θ Cu Kα).

In other embodiments, this disclosure relates to an alkylation processof producing mono-alkylaromatic compounds using a catalyst comprisingEMM-12 molecular sieve, wherein the EMM-12 molecular sieve has, in itsas-synthesized form and in calcined form, an X-ray diffraction patternincluding peaks at d-spacing maxima at 13.5±0.25, 12.33±0.23, andnon-discrete scattering between about 8.66 to 12.0 Angstroms or exhibita valley in between the peaks at 11.05±0.3 and 9.31±0.3 Angstroms butwith measured intensity corrected for background at the lowest pointbeing not less than 50% of the point at the same XRD d-spacing on theline connecting maxima at around 11.05±0.18 and 9.31±0.13 Angstroms.

In yet other embodiments, the mono-alkylaromatic compounds comprise atleast one of ethylbenzene, cumene and sec-butylbenzene.

In yet other embodiments, the process of this disclosure comprisescontacting an alkylating agent with an alkylatable aromatic compound inthe presence of a catalyst comprising EMM-12 under alkylation conditionsto form mono-alkylaromatic compounds.

These and other facets of the present invention shall become apparentfrom the following detailed description, Figures, and appended claims.

BRIEF DESCRIPTION OF THE FIGURE

FIG. 1 shows the XRD pattern between 5 to 11 degree 2-θ of Example 1.

DETAILED DESCRIPTION

Introduction

All patents, patent applications, test procedures (such as ASTM methods,UL methods, and the like), priority documents, articles, publications,manuals, and other documents cited herein are fully incorporated byreference to the extent such disclosure is not inconsistent with thepresent invention and for all jurisdictions in which such incorporationis permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.While the illustrative embodiments of the disclosure have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present disclosure,including all features which would be treated as equivalents thereof bythose skilled in the art to which the disclosure pertains.

As used in this specification, the term “framework type” is used in thesense described in the “Atlas of Zeolite Framework Types,” 2001.

As used herein, the numbering scheme for the Periodic Table Groups isused as in Chemical and Engineering News, 63(5), 27 (1985).

X-Ray Powder Diffraction Pattern

The interplanar spacings, d's, were calculated in Angstrom units (Å),and the relative intensities of the lines, I/I_(o), where the intensityof the strongest line above background, I_(o), is counted as 100, werederived with the use of a profile fitting routine (or second derivativealgorithm). The intensities are uncorrected for Lorentz and polarizationeffects. The relative intensities are given in terms of the symbolsVS=very strong (greater than 60 to 100), S=strong (greater than 40 to60), M=medium (greater than 20 to 40) and W=weak (0 to 20). It should beunderstood that diffraction data listed as single lines may consist ofmultiple overlapping lines which under certain conditions, such asdifferences in crystallographic changes, may appear as resolved orpartially resolved lines. Typically, crystallographic changes caninclude minor changes in unit cell parameters and/or a change in crystalsymmetry, without a change in the structure. These minor effects,including changes in relative intensities, can also occur as a result ofdifferences in cation content, framework composition, nature and degreeof pore filling, and thermal and/or hydrothermal history. Other changesin diffraction patterns can be indicative of important differencesbetween materials, which is the case for comparing MCM-22 with similarmaterials, e.g., MCM-49, MCM-56, and PSH-3.

The interplanar spacings, d's, were considered broad if they exhibitedpeak width of about 1.5° or more at half height determined as 50%intensity value from the maximum to the baseline.

The term “XRD distinguishable peak” as used herein is defined as XRDpeak with clearly defined peak maximum, which is at least two times ofthe average background noise level.

The term “non-discrete” peaks (also “unresolved” peaks) in XRD as usedherein means peaks having a monotonic profile in-between them(successive points either consistently increasing (or staying even) ordecreasing (or staying even) within noise).

The term “discrete” peaks (also “resolved” peaks) in XRD as used hereinmeans XRD peak(s) which are not non-discrete (unresolved).

FIG. 1 graphically demonstrates the XRD pattern between 5 to 11 degree2-θ of the product of Example 1. The measured intensity corrected forbackground at the lowest point between d-spacing maxima in the range of10.14 to 12.0 Angstroms and in the range from 8.66 to 10.13 Angstroms,represented as B, is the distance between the lowest point (point a) andthe point (point b) on the line of the background correction line at thesame XRD d-spacing of the lowest point (point a). The distance betweenthe point b and the point (point c) on the line connecting d-spacingmaxima in the range of 10.14 to 12.0 Angstroms and in the range from8.66 to 10.13 Angstroms at the same XRD d-spacing of the lowest point isrepresented as A.

Composition Matter of EMM-12

In some embodiments, the composition matter of EMM-12 has, inas-synthesized form and in calcined form, an X-ray diffraction patternincluding peaks having a d-spacing maximum in the range of 14.17 to12.57 Angstroms (˜6.15-7.05 deg 2-θ Cu Kα), such as, at 13.5±0.25, ad-spacing maximum in the range of 12.1 to 12.56 Angstroms (˜7.3-7.05 deg2-θ), such as, 12.33±0.23, and non-discrete scattering between about8.66 to 12.0 Angstroms or exhibit a valley in between the peaks having ad-spacing maximum in the range of 10.14 to 12.0 Angstroms (8.7-7.35 deg2-θ), such as, at 11.05±0.3, and a d-spacing maximum in the range from8.66 to 10.13 Angstroms (10.2-8.7 deg 2-θ), such as, at 9.31±0.3Angstroms, with measured intensity corrected for background at thelowest point being not less than 50% of the point at the same XRDd-spacing on the line connecting d-spacing maximum in the range of 10.14to 12.0 Angstroms (8.7-7.35 deg 2-θ) and d-spacing maximum in the rangefrom 8.66 to 10.13 Angstroms (10.2-8.7 deg 2-0).

In some embodiments, the composition matter of EMM-12 has, inas-synthesized form and in calcined form, an X-ray diffraction patternincluding peaks at d-spacing maxima at 13.5±0.25, 12.33±0.23, andnon-discrete scattering between about 8.85 to 11.05 Angstroms or exhibita valley in between the peaks at 11.05±0.3 and 9.31±0.3 Angstroms butwith measured intensity corrected for background at the lowest pointbeing not less than 50% of the point at the same XRD d-spacing on theline connecting maxima at around 11.05±0.18 and 9.31±0.13 Angstroms.

In further embodiments, the composition matter of EMM-12 further has, inas-synthesized form and in calcined form, an X-ray diffraction patternincluding peaks at d-spacing maxima at 3.57±0.06 and 3.43±0.06Angstroms. In yet further embodiments, the composition matter of EMM-12further has, in as-synthesized form and in calcined form, an X-raydiffraction pattern including peak at d-spacing maximum at 6.9±0.15Angstroms. In yet further embodiments, the composition matter of EMM-12further has, in as-synthesized form and in calcined form, an X-raydiffraction pattern including peak at d-spacing maximum at 3.96±0.08Angstroms.

In other embodiments, the composition matter of EMM-12 has, inas-synthesized form and in calcined form, an X-ray diffraction patternincluding peaks at d-spacing maxima and relative intensities at13.5±0.25 (M-VS), 12.33±0.23(M-VS), and non-discrete scattering betweenabout 8.85 to 11.05 Angstroms (W-S) or exhibit a valley in between thepeaks at 11.05±0.18 (W-S) and 9.31±0.13 (W-S) Angstroms but withmeasured intensity corrected for background at the lowest point beingnot less than 50% of the point at the same XRD d-spacing on the lineconnecting maxima at around 11.05±0.18 and 9.31±0.13 Angstroms.

TABLE 2 Interplanar Relative Intensity, d-Spacing (Å) I/I_(o) × 100 14.17 > d > 12.57 M-VS 12.56 > d > 12.1 M-VS  12.0 > d > 10.14 W-S10.13 > d > 8.66 W-S  6.9 ± 0.15 W-M, broad 3.96 ± 0.08 W-VS, broad 3.57± 0.06 W-M 3.43 ± 0.06 M-VS

In other embodiments, the composition matter of EMM-12 further has, inas-synthesized form and in calcined form, an X-ray diffraction patternincluding peaks at d-spacing maxima at 3.57±0.06 (W-M) and 3.43±0.06(M-VS) Angstroms. In yet further embodiments, the composition matter ofEMM-12 further has, in as-synthesized form and in calcined form, anX-ray diffraction pattern including peak at d-spacing maximum at6.9±0.15 Angstroms (W-M, broad). In yet further embodiments, thecomposition matter of EMM-12 further has, in as-synthesized form and incalcined form, an X-ray diffraction pattern including peak at d-spacingmaximum at 3.96±0.08 Angstroms (W-VS, broad).

In some preferred embodiments, the X-ray diffraction pattern of thecrystalline molecular sieve EMM-12 further has peaks at d-spacing maximaand intensities listed in Table 2.

In some embodiments, the X-ray diffraction pattern of the crystallinemolecular sieve EMM-12 of this disclosure further includes a d-spacingmaximum at 28±2 Angstroms.

In some embodiments, the EMM-12 exhibits an extraordinary high collidinenumber of greater than 150 μmoles/g, preferably greater than 200μmoles/g, more preferably greater than 250 μmoles/g, even morepreferably greater than 300 μmoles/g, and most preferably greater than350 μmoles/g, compared for up to about 200 μmoles/g for EMM-10 and 120μmoles/g for MCM-22.

Chemical Composition of As-Synthesized EMM-12 and Calcined EMM-12

The as-synthesized EMM-12 molecular sieve material of this disclosuremay have a composition, in terms of mole ratios of oxides:

-   -   YO₂/X₂O₃ in the range of 10 to infinity or in the range of 10 to        50;    -   M/X₂O₃ in the range of 0.005-0.1; and    -   R/X₂O₃ in the range of 1-4.

The calcined EMM-12 molecular sieve material of this disclosure may beprepared by calcining as-synthesized EMM-12 under calcination conditionsto remove at least the majority of the organic template R from theas-synthesized EMM-12.

Process of Making EMM-12

In some embodiments, this disclosure relates to a method ofmanufacturing an as-synthesized crystalline molecular sieve EMM-12, themethod comprising the steps of:

-   -   (a) providing a mixture comprising EMM-10-P family composition        and acidic composition, optionally a spacing agent;    -   (b) treating the mixture at treatment conditions to form a        product comprising as-synthesized EMM-12; and    -   (c) recovering the acid treated crystalline molecular sieve.

In some preferred embodiments, the as-synthesized EMM-12 is made by aprocess comprising:

-   -   (1) providing a mixture comprising EMM-10-P having Si/Al₂ in the        range from 10-infinity, preferable from about 10 to 150, and        acidic composition comprising at least one of nitric acid,        sulfuric acid, hydrochloric acid; oxalic acid, wherein said acid        has a concentration of less than or equal to 10 N, preferably        less than 1N, optionally a spacing agent comprising at least one        of dimethyldiethoxy silane, diethyldiethoxy silane, and        tetraethyl silane (TEOS), preferable TEOS; and    -   (2) treating the mixture of step (1) to treatment conditions,        wherein the treatment conditions comprise a temperature in the        range of 50-170° C. for a time in the range of 1-24 hrs,        optionally with a stirring speed in the range of 0-1000 RPM.

The mixture of step (a) comprises EMM-10-P family composition, acidiccomposition, and optionally a spacing agent, wherein the weight ratio ofthe solid content of the EMM-10-P family composition over the acidiccomposition and the weight ratio of the spacing agent over the solidcontent of the EMM-10-P family composition are listed in the followingtable (Table 3). Useful and preferred ranges of the treatmenttemperature and treatment time are also listed in Table 3.

TABLE 3 Useful Preferred Most preferred range range range Solid content(wt) 0.001-1000 0.01-100  0.1-10  Acidic composition Spacing agent (wt) 0-2 0-1  0.01-0.5  Solid content (wt) Acid concentration (N) 0.001-10 0.001-5    0.01-2    Temperature (° C.)  25-250 50-200 90-170 Time (hr)0.01-240 1-48 1-24

The following solid content over acidic composition weight ratios areuseful lower limits: 0.001, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 50, 100 and500. The following solid content over acidic composition weight ratiosare useful upper limits: 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 50, 100, 500and 1000. The solid content over acidic composition weight ratio fallsin a range between any one of the above-mentioned lower limits and anyone of the above-mentioned upper limits, so long as the lower limit isless than or equal to the upper limit. The solid content over acidiccomposition weight ratio may be present in an amount ranging from 0.01to 100 in one embodiment, alternatively 0.1 to 10, alternatively 0.1 to5.

The following ratios are useful lower spacing agent over solid contentweight ratio limits: 0, 0.001, 0.01, 0.05, 0.1, 0.5, 1, and 1.5. Thefollowing ratios are useful upper spacing agent over solid contentweight ratio limits: 0.001, 0.01, 0.05, 0.1, 0.5, 1, 1.5, and 2. Thespacing agent over solid content weight ratio falls in a range betweenany one of the above-mentioned lower spacing agent over solid contentweight ratio limits and any one of the above-mentioned upper spacingagent over solid content weight ratio limits, so long as the lowerspacing agent over solid content weight ratio limit is less than orequal to the upper spacing agent over solid content weight ratio limit.The spacing over solid content weight ratio may be present in an amountranging from 0 to 2 in one embodiment, alternatively 0 to 1, andalternatively 0.1 to 0.5.

The following temperatures (° C.) are useful lower treatment temperaturelimits: 25, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170,and 200. The following temperatures (° C.) are useful upper treatmenttemperature limits: 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150,160, 170, 180, 190, 200, 210, 220, 230, 240, and 250. The treatmenttemperature (° C.) falls in a range between any one of theabove-mentioned lower treatment temperature limits and any one of theabove-mentioned upper treatment temperature limits, so long as the lowertreatment temperature limit is less than or equal to the upper treatmenttemperature limit. The treatment temperature may be present in an amountranging from 25° C. to 250° C. in one embodiment, alternatively 70° C.to 200° C., and alternatively 90° C. to 170° C.

The following times (hr) are useful lower time limits for treatment:0.01, 1, 5, 10, 20, 30, 50, 100, and 150. The following time (hr) areuseful upper time limits for treatment: 1, 5, 10, 20, 40, 50, 70, 100,150, 200, and 240. The time (hr) for treatment falls in a range betweenany one of the above-mentioned lower time limits for treatment and anyone of the above-mentioned upper time limits for treatment, so long asthe lower time limit for treatment is less than or equal to the uppertime limit for treatment. The time for treatment may be present in anamount ranging from 1 to 100 in one embodiment, alternatively 1 to 48,and alternatively 1 to 24.

(1) EMM-10-P Family Composition

EMM-10-P family composition as used herein comprises at least one ofEMM-10-P composition disclosed in U.S. patent application Ser. No.11/823,129 (its entirety of which is enclosed herein by reference) andas-synthesized MCM-22 family molecular sieve composition disclosed inU.S. patent application Ser. No. 11/827,953 (its entirety of which isenclosed herein by reference).

The EMM-10-P composition relates to a crystalline molecular sieve,designated as EMM-10-P, having, in its as-synthesized form, an X-raydiffraction pattern including d-spacing maxima at 13.18±0.25 and12.33±0.23 Angstroms, wherein the peak intensity of the d-spacingmaximum at 13.18±0.25 Angstroms is at least as great as 90% of the peakintensity of the d-spacing maximum at 12.33±0.23 Angstroms. In addition,the X-ray diffraction pattern of the EMM-10-P molecular sieve furtherincludes two XRD distinguishable peaks with d-spacing maxima at11.06±0.18 and 9.25±0.13 Angstroms, wherein the peak intensity of thed-spacing maximum at 11.06±0.18 Angstroms is at least as great as thepeak intensity of the d-spacing maximum at 9.25±0.13 Angstroms.Additionally, the peaks with d-spacing maxima at 11.06±0.18 and9.25±0.13 Angstroms may be non-discrete peaks.

Further the EMM-10-P relates to a crystalline MCM-22 family molecularsieve that has a total surface area of greater than 450 m²/g as measuredby the N₂ BET method, and preferably has a ratio of the external surfacearea over the total surface area of less than 0.15 after conversion intoH-form by exchange with ammonium nitrate and calcination, wherein theexternal surface area is determined from a t-plot of the N₂ BET.

Additionally, the EMM-10-P relates to a MCM-22 family crystallinemolecular sieve that has a morphology of tabular habit, wherein at least50 wt % of the crystalline molecular sieve have a crystal diametergreater than 1 μm as measured by the SEM, preferably greater than 2 μmas measured by the SEM, preferably at least 50 wt % of the crystallinemolecular sieve have a crystal thickness of about 0.025 μm as measuredby the SEM.

U.S. patent application Ser. No. 11/827,953, its entirety of which isenclosed herein by reference, discloses a novel crystalline MCM-22family molecular sieve having, in its as-synthesized form, an X-raydiffraction pattern including a peak at d-spacing maximum of 12.33±0.23Angstroms, a distinguishable peak at a d-spacing maximum between 12.57to about 14.17 Angstroms and a non-discrete peak at a d-spacing maximumbetween 8.8 to 11 Angstroms, wherein the peak intensity of the d-spacingmaximum between 12.57 to about 14.17 Angstroms is less than 90% of thepeak intensity of the d-spacing maximum at 12.33±0.23 Angstroms.

The EMM-10-P as disclosed in U.S. patent application Ser. No.11/827,953, may be made by crystallizing a mixture having a compositionin molar ratio listed in Table 4.

TABLE 4 Reactants Useful Preferred YO₂/X₂O₃ 10 to infinity 15-55 H₂O/YO₂1 to 10000  5-35 OH⁻/YO₂* 0.001-0.39  0.1-0.35 OH⁻/YO₂** 0.001-0.590.1-0.5 M/YO₂ 0.001-2   0.1-1   R/YO₂ 0.001-2   0.01-0.5  Seed*** 0-25wt % 1-5 wt % R Me₆-diquat-5 salt(s) Me₆-diquat-5 salt(s)

After crystallization, the EMM-10-P product has a composition in molarratio listed in Table 5.

TABLE 5 Reactants Useful Preferred YO₂/X₂O₃ 10 to infinity M/X₂O₃0.005-0.1 R/X₂O₃  1-4 R Me₆-diquat-5 salt(s) Me₆-diquat-5 salt(s)

U.S. patent application Ser. No. 11/827,953, its entirety of which isenclosed herein by reference, discloses a novel crystalline MCM-22family molecular sieve. The as-synthesized composition disclosed in U.S.patent application Ser. No. 11/827,953 is a novel crystalline MCM-22family molecular sieve having, in its as-synthesized form, an X-raydiffraction pattern including a peak at d-spacing maximum of 12.33±0.23Angstroms, a distinguishable peak at a d-spacing maximum between 12.57to about 14.17 Angstroms and a non-discrete peak at a d-spacing maximumbetween 8.8 to 11 Angstroms, wherein the peak intensity of the d-spacingmaximum between 12.57 to about 14.17 Angstroms is less than 90% of thepeak intensity of the d-spacing maximum at 12.33±0.23 Angstroms. Theas-synthesized composition of U.S. patent application Ser. No.11/827,953 may further comprises XRD peaks at d-spacing maxima at3.57±0.06 and 3.43±0.06 Angstroms and/or a d-spacing maximum at 28±1Angstroms.

Furthermore, the X-ray diffraction pattern of the as-synthesizedcomposition of U.S. patent application Ser. No. 11/827,953 includesvalues and relative intensities substantially as shown in Table 6:

TABLE 6 Interplanar Relative Intensity, d-Spacing (Å) I/I_(o) × 10014.17 > d > 12.57 M-VS 12.33 ± 0.23  M-VS 11.1 to 8.8 W-S 4.41 ± 0.1 W-M, broad 3.96 ± 0.08 W-VS, broad 3.57 ± 0.06 W-M 3.43 ± 0.06 M-VS

The solid content of an EMM-10-P family composition used in the weightratio of the solid content of the EMM-10-P family composition over theacidic composition and the weight ratio of the spacing agent over thesolid content of the EMM-10-P family composition is calculated by thetotal weight of tetravalent element oxide and trivalent element oxide inan EMM-10-P family composition.

(2) Acidic Compositions

The acidic composition useful for this disclosure comprises an acidicsolute and a solvent. The acidic solute comprises at least one ofinorganic acid, such as, nitric acid hydrochloric acid and sulfuricacid, and organic acid, such as, oxalic acid and acetic acid, or anycombination of inorganic acid and organic acid. Preferably, the acidicsolute is nitric acid. The solvent comprises at least one of water,methanol, ethanol, acetone and dimethylsulfone (DMSO).

The acid concentration of the acidic composition is in the range of0.001 to 10. The following acid concentrations are useful lower limits:0.001, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, and 9. Thefollowing acid concentrations are useful upper limits: 0.01, 0.05, 0.1,0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. The acid concentration falls ina range between any one of the above-mentioned lower limits and any oneof the above-mentioned upper limits, so long as the lower limit is lessthan or equal to the upper limit. The acid concentration may be presentin an amount ranging from 0.001 to 5 in one embodiment, alternatively0.01 to 4, and alternatively 0.1 to 2.

The weight of acidic composition as used in the solid content overacidic composition weight ratios is calculated based on the total weightof acidic solute and solvent.

(3) Optional Spacing Agent

Optionally, the acidic treatment step also comprises a spacing agent.The spacing agent useful is any agent capable of providing a siliconmoiety that can stabilize the precursor in expanded form (i.e. havingthe distinct (002) peak at 13.5±0.25 in both as-synthesized and calcinedforms).

Examples of compounds for spacing include organo-compounds of atetravalent element, a trivalent element, and/or pentavalent compounds,such as, organosilicon compound, organogermanium compound, orgnotitaniumcompounds, organoboron compounds, organoaluminum compound, andorganophorphous compound. The organosilicon silicon compounds maycomprise a polysiloxane include silicones, a siloxane, and a silaneincluding disilanes and alkoxysilanes.

Silicone compounds that can be used in the present invention include thefollowing:

wherein R₁ is hydrogen, fluoride, hydroxy, alkyl, aralkyl, alkaryl orfluoro-alkyl. The hydrocarbon substituents generally contain from 1 toabout 10 carbon atoms and preferably are methyl or ethyl groups. R₂ isselected from the same group as R₁, and n is an integer of at least 2and generally in the range of 2 to about 1000. The molecular weight ofthe silicone compound employed is generally between about 80 to about20,000 and preferably about 150 to about 10,000. Representative siliconecompounds include dimethylsilicone, diethylsilicone,phenylmethylsilicone, methyl hydrogensilicone, ethylhydrogensilicone,phenylhydrogensilicone, fluoropropylsilicone,ethyltrifluoroprophysilicone, tetrachlorophenyl methylmethylethylsilicone, phenylethylsilicone, diphenylsilicone,methyltrisilicone, tetrachlorophenylethyl silicone, methylvinylsiliconeand ethylvinylsilicone. The silicone compound need not be linear but maybe cyclic as for example hexamethylcyclotrisiloxane,octamethylcyclotetrasiloxane, hexaphenyl cyclotrisiloxane andoctaphenylcyclotetrasiloxane. Mixtures of these compounds may also beused as well as silicones with other functional groups.

Useful siloxanes and polysiloxanes include as non-limiting examplehexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethytrisiloxane,decamethyltetrasiloxane, hexaethylcyclotrisiloxane, octaethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane andoctaphenylcyclo-tetrasiloxane.

Useful silanes, disilanes, or alkoxysilanes include organic substitutedsilanes having the general formula:

wherein R is a reactive group such as hydrogen, alkoxy, halogen,carboxy, amino, acetamide, trialkylsilyoxy, R₁, R₂ and R₃ can be thesame as R or can be an organic radical which may include alkyl of from 1to about 40 carbon atoms, alkyl or aryl carboxylic acid wherein theorganic portion of alkyl contains 1 to about 30 carbon atoms and thearyl group contains about 6 to about 24 carbons which may be furthersubstituted, alkylaryl and arylalkyl groups containing about 7 to about30 carbon atoms. Preferably, the alkyl group for an alkyl silane isbetween about 1 and about 4 carbon atoms in chain length. Mixtures mayalso be used.

The silanes or disilanes include, as non-limiting examples,dimethylphenylsilane, phenytrimethylsilane, triethylsilane andhexamethyldislane. Useful alkoxysilanes are those with at least onesilicon-hydrogen bond.

Alkylation Process

The term “aromatic” in reference to the alkylatable aromatic compoundswhich may be useful as feedstock herein is to be understood inaccordance with its art-recognized scope. This includes alkylsubstituted and unsubstituted mono- and polynuclear compounds. Compoundsof an aromatic character that possess a heteroatom may also be usefulprovided sufficient catalytic activity is maintained under the reactionconditions selected.

Substituted aromatic compounds that can be alkylated herein must possessat least one hydrogen atom directly bonded to the aromatic nucleus. Thearomatic rings can be substituted with one or more alkyl, aryl, alkaryl,alkoxy, aryloxy, cycloalkyl, halide, and/or other groups that do notinterfere with the alkylation reaction.

Suitable aromatic compounds include benzene, naphthalene, anthracene,naphthacene, perylene, coronene, and phenanthrene, with benzene beingpreferred.

Generally the alkyl groups that may be present as substituents on thearomatic compound contain from 1 to about 22 carbon atoms and usuallyfrom about 1 to 8 carbon atoms, and most usually from about 1 to 4carbon atoms.

Suitable alkyl substituted aromatic compounds include toluene, xylene,isopropylbenzene, n-propylbenzene, alpha-methylnaphthalene,ethylbenzene, mesitylene, durene, cymenes, butylbenzene, pseudocumene,o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, isoamylbenzene,isohexylbenzene, pentaethylbenzene, pentamethylbenzene;1,2,3,4-tetraethylbenzene; 1,2,3,5-tetramethylbenzene;1,2,4-triethylbenzene; 1,2,3-trimethylbenzene, m-butyltoluene;p-butyltoluene; 3,5-diethyltoluene; o-ethyltoluene; p-ethyltoluene;m-propyltoluene; 4-ethyl-m-xylene; dimethylnaphthalenes;ethylnaphthalene; 2,3-dimethylanthracene; 9-ethylanthracene;2-methylanthracene; o-methylanthracene; 9,10-dimethylphenanthrene; and3-methyl-phenanthrene. Higher molecular weight alkylaromatic compoundscan also be used as starting materials and include aromatic organicssuch as are produced by the alkylation of aromatic organics with olefinoligomers. Such products are frequently referred to in the art asalkylate and include hexylbenzene, nonylbenzene, dodecylbenzene,pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene,pentadecytoluene, etc. Very often alkylate is obtained as a high boilingfraction in which the alkyl group attached to the aromatic nucleusvaries in size from about C₆ to about C₁₂. When cumene or ethylbenzeneis the desired product, the present process produces acceptably littleby-products such as n-propyl benzene and xylenes respectively. Theseby-products made in such instances may be less than about 100 wppm.

Reformate containing a mixture of benzene, toluene and/or xyleneconstitutes a particularly useful feed for the alkylation process ofthis disclosure.

The alkylating agents that may be useful in the process of thisdisclosure generally include any aliphatic or aromatic organic compoundhaving one or more available alkylating aliphatic groups capable ofreaction with the alkylatable aromatic compound, preferably with thealkylating group possessing from 1 to 5 carbon atoms. Examples ofsuitable alkylating agents are olefins such as ethylene, propylene, thebutenes such as, for example, 1-butene, 2-butene or isobutylene, and thepentenes; alcohols (inclusive of monoalcohols, dialcohols, trialcohols,etc.) such as methanol, ethanol, the propanols, the butanols, and thepentanols; aldehydes such as formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, and n-valeraldehyde; and alkyl halidessuch as methyl chloride, ethyl chloride, the propyl chlorides, the butylchlorides, and the pentyl chlorides, alkylaromatic compounds, such as,trimethylbenzenes, di-ethylbenzenes, triethylbenzenes, and so forth.Mixtures of these compounds may also be useful, such as, for example,propylene and propanol mixtures.

Mixtures of light olefins are useful as alkylating agents in thealkylation process of this disclosure. Accordingly, mixtures ofethylene, propylene, butenes, and/or pentenes which are majorconstituents of a variety of refinery streams, e.g., fuel gas, gas plantoff-gas containing ethylene, propylene, etc., naphtha cracker off-gascontaining light olefins, refinery FCC propane/propylene streams, etc.,are useful alkylating agents. For example, a typical FCC light olefinstream possesses the following composition:

Wt. % Mole % Ethane 3.3 5.1 Ethylene 0.7 1.2 Propane 4.5 15.3 Propylene42.5 46.8 Isobutane 12.9 10.3 n-Butane 3.3 2.6 Butenes 22.1 18.32Pentanes 0.7 0.4

Reaction products that may be obtained from the process of the presentdisclosure include ethylbenzene from the reaction of benzene withethylene, cumene from the reaction of benzene with propylene,ethyltoluene from the reaction of toluene with ethylene, cymenes fromthe reaction of toluene with propylene, and sec-butylbenzene from thereaction of benzene and n-butenes. Particularly preferred processmechanisms of the disclosure relate to the production of cumene by thealkylation of benzene with propylene and production of ethylbenzene bythe alkylation of benzene with ethylene.

The reactants can be partially or completely in the liquid phase and canbe neat, i.e. free from intentional admixture or dilution with othermaterial, or they can be brought into contact with the catalystcomposition with the aid of carrier gases or diluents such as, forexample, hydrogen, methane and/or nitrogen.

The alkylation process of this disclosure may be conducted such that theorganic reactants, i.e., the alkylatable aromatic compound and thealkylating agent, are brought into contact with the presently requiredcatalyst in a suitable reaction zone under effective alkylationconditions. Such conditions include a temperature of from about 0° C. toabout 500° C., preferably from about 10° C. to about 260° C., a pressureof from about 20 to about 25000 kPa-a, preferably from about 100 toabout 5500 kPa-a, a molar ratio of alkylatable aromatic compound toalkylating agent of from about 0.1:1 to about 50:1, preferably fromabout 0.5:1 to about 10:1, and a feed weight hourly space velocity(WHSV) based on the alkylating agent of from about 0.1 to 500 hr⁻¹,preferably from about 0.1 to about 100 hr⁻¹.

When benzene is alkylated with ethylene to produce ethylbenzene, thealkylation reaction is preferably carried out in the liquid phase underconditions including a temperature of from about 150° C. to about 300°C., more preferably from about 170° C. to about 260° C.; a pressure upto about 20400 kPa-a, more preferably from about 2000 kPa-a to about5500 kPa-a; a weight hourly space velocity (WHSV) based on the ethylenealkylating agent of from about 0.1 to about 20 hr⁻¹, more preferablyfrom about 0.5 to about 6 hr⁻¹; and a ratio of benzene to ethylene inthe alkylation reaction zone of from about 0.5:1 to about 100:1 molar,preferably 0.5:1 to 50:1 molar, more preferably from about 1:1 to about30:1 molar, most preferably from about 1:1 to about 10:1 molar.

When benzene is alkylated with propylene to produce cumene, the reactionmay also take place under liquid phase conditions including atemperature of up to about 250° C., preferably up to about 150° C.,e.g., from about 10° C. to about 125° C.; a pressure of about 25000kPa-a or less, e.g., from about 100 to about 3000 kPa-a; a weight hourlyspace velocity (WHSV) based on propylene alkylating agent of from about0.1 hr⁻¹ to about 250 hr⁻¹, preferably from about 1 hr⁻¹ to about 50hr⁻¹; and a ratio of benzene to propylene in the alkylation reactionzone of from about 0.5:1 to about 100:1 molar, preferably 0.5:1 to 50:1molar, more preferably from about 1:1 to about 30:1 molar, mostpreferably from about 1:1 to about 10:1 molar.

When benzene is alkylated with a butene to produce sec-butylbenzene, thereaction may also take place under liquid phase conditions including atemperature of up to about 250° C., preferably up to about 150° C.,e.g., from about 10° C. to about 125° C.; a pressure of about 25000kPa-a or less, e.g., from about 1 to about 3000 kPa-a; a weight hourlyspace velocity (WHSV) based on the butene alkylating agent of from about0.1 hr⁻¹ to about 250 hr⁻¹, preferably from about 1 hr⁻¹ to about 50hr⁻¹; and a ratio of benzene to butene in the alkylation reaction zoneof from about 0.5:1 to about 100:1 molar, preferably 0.5:1 to 50:1molar, more preferably from about 1:1 to about 30:1 molar, mostpreferably from about 1:1 to about 10:1 molar.

A summary of the molecular sieves and/or zeolites, in terms ofproduction, modification and characterization of molecular sieves, isdescribed in the book “Molecular Sieves—Principles of Synthesis andIdentification”; (R. Szostak, Blackie Academic & Professional, London,1998, Second Edition). In addition to molecular sieves, amorphousmaterials, chiefly silica, aluminum silicate and aluminum oxide, havebeen used as adsorbents and catalyst supports. A number of long-knownforming techniques, like spray drying, pilling, pelletizing andextrusion, have been and are being used to produce macrostructures inthe form of, for example, spherical particles, extrudates, pellets andTablets of both micropores and other types of porous materials for usein catalysis, adsorption and ion exchange. A summary of these techniquesis described in “Catalyst Manufacture,” A. B. Stiles and T. A. Koch,Marcel Dekker, New York, 1995.

To the extent desired, the original metal cations of the as-synthesizedmaterial can be replaced in accordance with techniques well known in theart, at least in part, by ion exchange with other cations. Preferredreplacing cations include metal ions, hydrogen ions, hydrogen precursor,e.g., ammonium, ions and mixtures thereof. Particularly preferredcations are those which tailor the catalytic activity for certainhydrocarbon conversion reactions. These include hydrogen, rare earthmetals and metals of Groups 1-17, preferably Groups 2-12 of the PeriodicTable of the Elements.

The EMM-12 crystalline molecular sieve of this disclosure should begenerally dehydrated, at least partially. This can be done by heating toa temperature in the range of e.g., 200° C. to 595° C. in an atmospheresuch as air or nitrogen, and at atmospheric, sub-atmospheric orsuper-atmospheric pressures for e.g., between 30 minutes and 48 hours.The degree of dehydration is measured by the percentage of weight lossrelative to the total weight loss of a molecular sieve sample at 595° C.under flowing dry nitrogen (less than 0.001 kPa partial pressure ofwater vapor) for 48 hours. Dehydration can also be performed at roomtemperature (˜25° C.) merely by placing the silicate in a vacuum, but alonger time is required to obtain a sufficient amount of dehydration.

The EMM-12 crystalline molecular sieve of this disclosure especially inits metal, hydrogen and ammonium forms can be beneficially converted toanother form by thermal treatment. This thermal treatment is generallyperformed by heating one of these forms at a temperature of at least370° C. for at least one minute and generally not longer than 1000hours. While sub-atmospheric pressure can be employed for the thermaltreatment, atmospheric pressure is desired for reasons of convenience.The thermal treatment can be performed at a temperature up to about 925°C. The thermal treated product is particularly useful in the catalysisof certain hydrocarbon conversion reactions. The thermally treatedproduct, especially in its metal, hydrogen and ammonium forms, isparticularly useful in the catalysis of certain organic, e.g.,hydrocarbon, conversion reactions. Non-limiting examples of suchreactions include those described in U.S. Pat. Nos. 4,954,325;4,973,784; 4,992,611; 4,956,514; 4,962,250; 4,982,033; 4,962,257;4,962,256; 4,992,606; 4,954,663; 4,992,615; 4,983,276; 4,982,040;4,962,239; 4,968,402; 5,000,839; 5,001,296; 4,986,894; 5,001,295;5,001,283; 5,012,033; 5,019,670; 5,019,665; 5,019,664; and 5,013,422,each incorporated herein by reference as to the description of thecatalytic reactions.

The EMM-12 crystalline molecular sieve of this disclosure can be shapedinto a wide variety of particle sizes. Generally speaking, the particlescan be in the form of a powder, a granule, or a molded product, such asan extrudate. In cases where the catalyst is molded, such as byextrusion, the crystals can be extruded before drying or partially driedand then extruded.

It is desired to incorporate the EMM-12 molecular sieve with anothermaterial resistant to the temperatures and other conditions employed inalkylation processes. Such materials include active and inactivematerials and synthetic or naturally occurring zeolites as well asinorganic materials such as clays, silica and/or metal oxides such asalumina. The latter may be either naturally occurring or in the form ofgelatinous precipitates or gels including mixtures of silica and metaloxides. Use of a material in conjunction with the EMM-12 molecularsieve, i.e. combined therewith or present during synthesis of the EMM-12molecular sieve, which is active, tends to change the conversion and/orselectivity of the catalyst. Inactive materials suitably serve asdiluents to control the amount of conversion in a given process so thatproducts can be obtained economically and orderly without employingother means for controlling the rate of reaction. These materials may beincorporated into naturally occurring clays, e.g., bentonite and kaolin,to improve the crush strength of the catalyst under commercial operatingconditions. The materials, i.e. clays, oxides, etc., function as bindersfor the catalyst. It is desirable to provide a catalyst having goodcrush strength because in commercial use it is desirable to prevent thecatalyst from breaking down into powder-like materials. These claybinders have been employed normally only for the purpose of improvingthe crush strength of the catalyst.

Naturally occurring clays which can be composited with the EMM-12molecular sieve include the montmorillonite and kaolin family, whichfamilies include the subbentonites, and the kaolins commonly known asDixie, McNamee, Georgia and Florida clays or others in which the mainmineral constituent is halloysite, kaolinite, dictite, narcite, oranauxite. Such clays can be used in the raw state as originally mined orinitially subjected to calcination, treatment or chemical modification.Binders useful for compositing with the present crystal also includeinorganic oxides, notably alumina.

In addition to the foregoing materials, the EMM-12 molecular sieve canbe composited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of finely divided EMM-12 crystalline molecularsieve and inorganic oxide matrix vary widely, with the crystal contentranging from about 1 to about 99 percent by weight and more usually,particularly when the composite is prepared in the form of beads, in therange of about 20 to about 80 wt % of the composite.

The following examples reflect embodiments of the invention and are byno means intended to be limiting of the scope of the invention.

Experiments

Powder X-Ray Diffraction

Powder x-ray data were obtained on a Bruker D4 instrument inBragg-Brentano geometry with monochromatic Cu Kα radiation. The patternused for structural characterization extended from 1.2 to 80° in 2θ.Intensities for Rietveld refinement were extracted from the continuousscans.

Surface Areas

The overall surface area of a molecular sieve may be measured by theBrunauer-Emmett-Teller (BET) method using adsorption-desorption ofnitrogen (temperature of liquid nitrogen, 77 K). The internal surfacearea may be calculated using t-plot of the Brunauer-Emmett-Teller (BET)measurement. The external surface area is calculated by subtracting theinternal surface area from the overall surface area measured by theBrunauer-Emmett-Teller (BET) measurement.

Collidine Number Measurement

The collidine number of a molecular sieve may be measured by TGA. Asample is dried at 200° C. to constant weight (weight change less than±1% for the period of 1 hour). The weight of the dried sample, thesorbate, is then measured. The sorbent, 2,4,6-collidine, is delivered bya sparger maintained at 3 Torr collidine partial pressure and carriedover the sample by nitrogen passed 200 ml/min for 60 min. The collidinenumber is expressed as micromoles of adsorbed per gram of the sorbate.

Example 1 Preparation of EMM-12

A sample of EMM-10-P (1.5 g) made according to Example 1 of U.S. patentapplication Ser. No. 11/823,129 was added to the mixture of 30 g of 1 Mnitric acid and 0.3 g of diethoxydimethylsilane. The reaction wascarried out in a teflon container sealed in a Parr™ bomb in the oven at170° C. for 24 hrs. The solid product of EMM-12 was isolated byfiltration, washed and dried at 120° C.

The XRD pattern of the solid product of EMM-12 is characterized ascomprising a doublet at between 12.45 and 13.60 Angstroms, correspondingto 6.5-7.1°2θ (Cu Kα) and non-discrete scattering between 8.85 to 11.05Angstroms, the 8-10°2θ (Cu Kα) region or exhibit a valley in between thepeaks at 11.05±0.18 and 9.31±0.13 Angstroms but with measured intensitycorrected for background at the lowest point being not less than 50% ofthe point at the same XRD d-spacing on the line connecting maxima ataround 11.05±0.18 and 9.31±0.13 Angstroms.

The calcined product of EMM-12 has high surface area of 523 m²/g andextraordinary enhancement of collidine adsorption of 321 μmoles/g.

Benzene

Benzene was obtained from a commercial source. The benzene was passedthrough a pretreatment vessel containing equal parts (by volume)molecular sieve 13X, molecular sieve 4A, Engelhard F-24 Clay, andSelexsorb CD (in order from inlet to outlet), and then through apretreatment vessel containing MCM-22 catalyst. All feed pretreatmentmaterials were dried in a 260° C. oven for 12 hours before using.

Propylene

Propylene was obtained from a commercial specialty gases source and waspolymer grade.

Ethylene

Ethylene was obtained from a commercial specialty gases source and waspolymer grade.

Nitrogen

Nitrogen was ultra high purity grade and obtained from a commercialspecialty gases source.

Example 2

A 65 wt. % EMM-12 calcined of Example 1 and 35 wt. % alumina catalystwas prepared. This catalyst was tested for benzene alkylation withpropylene to form cumene.

Feed Pretreatment

The experiment was conducted in a fixed bed ⅜″ OD tubular reactor in adownflow configuration with an ⅛″ internal thermocouple. The reactorfurnace was controlled in isothermal mode. Two grams of catalyst sizedto 14/20 mesh was loaded into the ⅜″ reactor. Experiment was conductedwith catalyst loaded into the ⅜″ reactor. The catalyst bed was axiallycentered in the middle furnace zone. The catalyst was packed with inertsand to fill the interstitial void spaces. Reaction conditions were 130°C., 2169 kPa-a and the benzene/propylene molar ratio was 3/1. Weighthourly space velocity was 1 hr⁻¹ on a propylene basis.

At reactor start-up, the reactor was brought to reaction pressure of2169 kPa-a with the ultra high purity nitrogen, and heated to reactiontemperature of 150° C. prior to introducing the benzene feed for 24hours. The catalyst was allowed to equilibrate for 1 day prior tointroducing the propylene to achieve steady state before data wascollected. The reactor was cooled to 130° C. under benzene flow and thenpropylene was introduced. Products were collected and analyzed for 13days on-stream. Results shows that Diisopropylbenzene (DIPB) over cumene(isopropylbenzene, IPB) molar ratios of the products fall in the rangeof 10% to 14%.

Example 3

One gram of pellet of 65 wt. % EMM-12 and 35 wt. % Versal 300 alumina(commercially available from UOP) was used for benzene alkylation withethylene to form ethylbenzene. The catalyst was calcined for 2 hours at538° C.

Benzene alkylation with ethylene was conducted by charging a fixedweight of catalyst to a well-mixed Parr autoclave reactor along with amixture comprising benzene and ethylene (benzene/ethylene ratio of 3.5molar). The reaction was carried out at 220° C. and 3893 KPa-a (550psig) for 4 hours. A small sample of the product was withdrawn atregular intervals and analyzed by gas chromatography. The catalystperformance was assessed by a kinetic activity rate constant anddiethylbenzene/ethylbenzene weight ratio after 4 hours. The EMM-12catalyst has an activity of 2 (hr·gmole/cc)⁻¹ and a selectivity of 5.3measured by diethylbenzene/ethylbenzene weight ratio.

We claim:
 1. A process for manufacturing a mono-alkylaromatic compound,said process comprising contacting a feedstock comprising an alkylatablearomatic compound and an alkylating agent under alkylation reactionconditions with a catalyst comprising a molecular sieve to form saidmono-alkylaromatic compound, said molecular sieve having, in itsas-synthesized form and in calcined form, an X-ray diffraction patternincluding peaks having a d-spacing maximum in the range of 14.17 to12.57 Angstroms, a d-spacing maximum in the range of 12.1 to 12.56Angstroms, and non-discrete scattering between about 8.85 to 11.05Angstroms or exhibit a valley in between the peaks having a d-spacingmaximum in the range of 10.14 to 12.0 Angstroms and a d-spacing maximumin the range from 8.66 to 10.13 Angstroms with measured intensitycorrected for background at the lowest point being not less than 50% ofthe point at the same X-ray diffraction d-spacing on the line connectingmaxima in the range of 10.14 to 12.0 Angstroms and in the range from8.66 to 10.13 Angstroms.
 2. The process of claim 1, wherein saidmolecular sieve further has, in its as-synthesized form and in calcinedform, an X-ray diffraction pattern including peaks at 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms.
 3. The process of claim 1, whereinsaid molecular sieve has a composition involving the molar relationship:X₂O₃:(n)YO₂, wherein X is a trivalent element comprises at least one ofaluminum, boron, iron and gallium, Y is a tetravalent element comprisesat least one of silicon and germanium, and n is at least about
 10. 4.The process of claim 3, wherein said molecular sieve, in theas-synthesized form, has a formula, on an anhydrous basis and in termsof moles of oxides per n moles of YO₂, as follows:(0.005−1)M₂O:(1−4)R:X₂O₃ :nYO₂ wherein M is an alkali or alkaline earthmetal, and R is an organic moiety.
 5. The process of claim 3, whereinsaid n is from about 10 to about
 150. 6. The process of claim 3, whereinX is aluminum and Y is silicon.
 7. The process sieve of claim 1, whereinsaid molecular sieve has a collidine adsorption capacity of at least 150μmmoles/g.
 8. The process of claim 1, wherein said alkylatable aromaticcompound is selected from the group consisting of benzene, naphthalene,anthracene, naphthacene, perylene, coronene, phenanthrene, xylene,n-propylbenzene, alpha-methylnaphthalene, o-diethylbenzene,m-diethylbenzene, p-diethylbenzene, pentaethylbenzene,pentamethylbenzene; 1,2,3,4-tetraethylbenzene;1,2,3,5-tetramethylbenzene; 1,2,4-triethylbenzene;1,2,3-trimethylbenzene, m-butyltoluene; p-butyltoluene;3,5-diethyltoluene; o-ethyltoluene; p-ethyltoluene; m-propyltoluene;4-ethyl-m-xylene; dimethylnaphthalenes; ethylnaphthalene;2,3-dimethylanthracene; 9-ethylanthracene; 2-methylanthracene;o-methylanthracene; 9,10-dimethylphenanthrene; 3-methyl-phenanthrene andmixtures thereof.
 9. The process of claim 1, wherein said alkylatablearomatic compound comprises at least one of benzene and naphthalene. 10.The process of claim 1, wherein said alkylating agent is selected fromthe group consisting of olefins, alcohols, aldehydes, alkyl halides andmixtures thereof.
 11. The process of claim 1, wherein said alkylatingagent comprises at least one of ethylene, propylene and butenes.
 12. Theprocess of claim 1, wherein said alkylation reaction conditions includea temperature of from about 0° C. to about 500° C., a pressure of fromabout 20 to about 25000 kPa-a, a molar ratio of alkylatable aromaticcompound to alkylating agent of from about 0.1:1 to about 50:1, and afeed weight hourly space velocity (WHSV) based on the alkylating agentof from about 0.1 to 500 hr⁻¹.
 13. The process of claim 1, wherein saidalkylatable aromatic compound comprises benzene, said alkylating agentcomprises ethylene, said mono-alkylaromatic compound comprisesethylbenzene, said alkylation reaction conditions include a temperatureof from about 150° C. to about 300° C., a pressure of from about 2000 toabout 5500 kPa-a, a molar ratio of alkylatable aromatic compound toalkylating agent of from about 0.5:1 to about 50:1, and a feed weighthourly space velocity (WHSV) based on the alkylating agent of from about0.1 to 20 hr⁻¹.
 14. The process of claim 1, wherein said alkylatablearomatic compound comprises benzene, said alkylating agent comprisespropylene, said mono-alkylaromatic compound comprises cumene, saidalkylation reaction conditions include a temperature of from about 10°C. to about 250° C., a pressure of from about 100 to about 3000 kPa-a, amolar ratio of alkylatable aromatic compound to alkylating agent of fromabout 0.5:1 to about 50:1, and a feed weight hourly space velocity(WHSV) based on the alkylating agent of from about 0.1 to 250 hr⁻¹. 15.The process of claim 1, wherein said alkylatable aromatic compoundcomprises benzene, said alkylating agent comprises butylene, saidmono-alkylaromatic compound comprises sec-butylbenzene, said alkylationreaction conditions include a temperature of from about 10° C. to about250° C., a pressure of from about 1 to about 3000 kPa-a, a molar ratioof alkylatable aromatic compound to alkylating agent of from about 0.5:1to about 50:1, and a feed weight hourly space velocity (WHSV) based onthe alkylating agent of from about 0.1 to 250 hr⁻¹.
 16. A process formanufacturing a mono-alkylaromatic compound, said process comprisingcontacting a feedstock comprising an alkylatable aromatic compound andan alkylating agent under alkylation reaction conditions with a catalystcomprising EMM-12 to form said mono-alkylaromatic compound, said EMM-12having, in its as-synthesized form and in calcined form, an X-raydiffraction pattern including peaks having a d-spacing maximum in therange of 14.17 to 12.57 Angstroms, a d-spacing maximum in the range of12.1 to 12.56 Angstroms, and non-discrete scattering between about 8.85to 11.05 Angstroms or exhibit a valley in between the peaks having ad-spacing maximum in the range of 10.14 to 12.0 Angstroms and ad-spacing maximum in the range from 8.66 to 10.13 Angstroms withmeasured intensity corrected for background at the lowest point beingnot less than 50% of the point at the same X-ray diffraction d-spacingon the line connecting maxima in the range of 10.14 to 12.0 Angstromsand in the range from 8.66 to 10.13 Angstroms.